【摘要】 本文成功地将取代苯胺的偶极短与其取代基常数σ相互关联起来,并发现在一定的条件下取代苯胺的熔点与后者也有良好的直线相互关系.证明了将本文所得σ^-值用之于苯胺在红外吸收光谱中的直线相互关系较旧有的最适合的σ值在相关系数上有改进,并将这些直线关系中的一部分推广到近红外区;成功地将取代苯胺在紫外吸收光谱中有相反的电子效应的取代基对其共轭光谱带的影响用本文所得?值归并在同一直线相互关系上,且其相关系数胜过用其他各种类似的取代基常数;再则共主光谱带与其相应克分子折射率也有良好直线相互关系.无须选用特殊的σ值和仅直接采用本文的σ^-值即能适用于取代苯胺在核磁共振谱中有关其氨基氢的化学位移的直线相互关系中,且其相关系数较旧有值有改进.为了尝试以σ^-与σ_I.R.^-相结合俾适合应用于芳香亲核取代反应的直线自由能关系中,已将现有数据逐一运算,并发现其实用价值与Miller所采用的数值不相上下.更多还原

【Abstract】 ABSTRACT This paper successfully correlated the dipole moments of substituted anilines with σ constants of the corresponding substituents and showed that under certain conditions the melting points of substituted anilines likewise have good linear correlation with the same set of constants. It is shown that the application of the σ^- values obtained in this work to the linear correlation of anilines in the infrared absorption spectra improved values on cor-relation coefficients as compared with those obtained by using the most suitable set of σ values hitherto available and that part of these linear correlations could be extended to the near infra-red region. It succeeded in bringing together the influences of substituents of opposite electronic effects of substituted anilines on the conjugation bands in the ultraviolet absorption spec-tra into a single linear correlation by using the ? values obtained in this work.The resulting correlation coefficient excelled those obtained through various other similar sets of sub-stituent constants and,furthermore,the principal electronic bands of these compounds also had good linear correlation with their corresponding molar refractive indices. Without requiring the selection of specially exceptional σ values,the σ^- values of this work can be applied directly to the linear correlation of chemical shifts of the amino hydrogen in the nuclear magnetic resonance spectra of substituted anilines.The correlation coefficients thus obtained are obviously improved in comparison with the existing values. In an attempt to extend the application to the linear free energy relationship of the nucleophilic aromatic substitution by using σ^- and σ_I.R.^- in combination,all available literature values on this subject have each been recalculated,and it is found that the practical value of these σ^- constants is just as good as that of those adopted by J.Miller in the same field.更多还原